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In the context of global warming, the Clausius–Clapeyron (CC) relationship has been widely used as an indicator of the evolution of the precipitation regime, including daily and sub-daily extremes. This study aims to verify the existence of links between precipitation extremes and 2 m air temperature for the Ottawa River Basin (ORB, Canada) over the period 1981–2010, applying an exponential relationship between the 99th percentile of precipitation and temperature characteristics. Three simulations of the Canadian Regional Climate Model version 5 (CRCM5), at three different resolutions (0.44°, 0.22°, and 0.11°), one simulation using the recent CRCM version 6 (CRCM6) at “convection-permitting” resolution (2.5 km), and two reanalysis products (ERA5 and ERA5-Land) were used to investigate the CC scaling hypothesis that precipitation increases at the same rate as the atmospheric moisture-holding capacity (i.e., 6.8%/°C). In general, daily precipitation follows a lower rate of change than the CC scaling with median values between 2 and 4%/°C for the ORB and with a level of statistical significance of 5%, while hourly precipitation increases faster with temperature, between 4 and 7%/°C. In the latter case, rates of change greater than the CC scaling were even up to 10.2%/°C for the simulation at 0.11°. A hook shape is observed in summer for CRCM5 simulations, near the 20–25 °C temperature threshold, where the 99th percentile of precipitation decreases with temperature, especially at higher resolution with the CRCM6 data. Beyond the threshold of 20 °C, it appears that the atmospheric moisture-holding capacity is not the only determining factor for generating precipitation extremes. Other factors need to be considered, such as the moisture availability at the time of the precipitation event, and the presence of dynamical mechanisms that increase, for example, upward vertical motion. As mentioned in previous studies, the applicability of the CC scaling should not be generalised in the study of precipitation extremes. The time and spatial scales and season are also dependent factors that must be taken into account. In fact, the evolution of precipitation extremes and temperature relationships should be identified and evaluated with very high spatial resolution simulations, knowing that local temperature and regional physiographic features play a major role in the occurrence and intensity of precipitation extremes. As precipitation extremes have important effects on the occurrence of floods with potential deleterious damages, further research needs to explore the sensitivity of projections to resolution with various air temperature and humidity thresholds, especially at the sub-daily scale, as these precipitation types seem to increase faster with temperature than with daily-scale values. This will help to develop decision-making and adaptation strategies based on improved physical knowledge or approaches and not on a single assumption based on CC scaling.